HERON rearrangement of N,N'-diacyl-N,N'-dialkoxyhydrazines a - Theoretical and experimental study

Article abstract of DOI:10.1016/S0040-4020(98)01151-X

Ab initio calculations at the B3LYP/6-31G* level on N-methoxy-N- dimethylaminoformamide and its rearrangement to methyl formate and 1,1- dimethyldiazene through the HERON reaction, have been carded out in conjunction with an experimental study of the HERON reactions of N,N'- diacyl-N,N'-dialkoxyhydrazines. Substituent effects are in accord with the theoretical properties of the transition state and point to an anomerically driven process in which donor groups on the anomeric nitrogen and withdrawing groups on the migrating alkoxy oxygen facilitate the rearrangement process.